Cationic cellulose derivatives of controlled charge density useful in cosmetic preparations

ABSTRACT

Water-soluble quaternary ammonium cellulosic derivatives of controlled charge density are disclosed. These derivatives are useful in cosmetic preparations, such as hair and skin formulations, for example hair conditioners. These quaternized cellulosic derivatives are useful as thickeners, conditioners, film formers, fixatives, emulsifiers, or additives in hair or skin formulations to improve combing, manageability, body, curl retention, moisture resistance, and binding of ingredients to keratin. Compared to existing agents, these compounds have improved temperature stability, improved interactions with surfactants (such as in shampoos), improved binding to keratin, improved mechanical properties, and can mend split ends on hair. A major advantage of these compounds is that they may be applied to hair directly from an aqueous solution, and do not require a volatile organic compound solvent as carrier. Alternatively, smaller amounts of VOC&#39;s may be used than is the case in current products, to improve drying times for the formulations. The compounds are also useful as antistatic agents, bactericides, flocculating agents, and as drug binding or drug delivery agents.

This is a divisional of co-pending application Ser. No. 08/822,987,filed Mar. 21, 1997; which claims the benefit of the Mar. 29, 1996filing date of the provisional application that was originally filed asnon-provisional application Ser. No. 08/623,675, and was later convertedto provisional status.

This invention pertains to polymers that are useful in cosmeticpreparations, particularly to cationic cellulose derivatives ofcontrolled charge density that are useful in hair care preparations.

BACKGROUND OF THE INVENTION

Naturally-occurring polymers such as tragacanth, arabic, or karaya gumswere used in early hair fixative products. These fixatives weretypically delivered from either an aqueous or a hydroalcoholic mediumonto damp hair. The hair was then styled and allowed to dry on rollers.This type of product was insufficient for all hairstyles, and animproved, quick drying product was developed, commonly known as hairspray.

Shellac was the first polymer used in hair sprays. Difficulties withshellac led to the use of synthetic resins instead--for example,polyvinylpyrrolidone (PVP), dimethylhydantoin formaldehyde (DMHF),PVP-vinyl acetate copolymer (PVP-VA), andpolyvinylpyrrolidone-methylmethacrylate-methacrylic acid terpolymer.Ongoing efforts in the cosmetics industry to synthesize new polymericresins have been driven by consumer demand for fixative products thatare resistant to humidity, but that still may be removed easily uponshampooing.

The use of chlorofluorocarbons in hairsprays has been banned in theUnited States since 1979. Many hair fixatives are currently applied in avolatile organic compound ("VOC") carrier. As the use of VOC's becomesmore restricted, there is an unfilled need for hair fixatives that maybe applied with little or no VOC's. It would be desirable to devise asystem in which water could replace some or all of the alcohol orpropellant that is used in current formulations. Such a substitutionpresents a similar challenge to that faced by formulators over fiftyyears ago: how to produce a quick-drying fixative product that isresistant to humidity and that may be easily removed in an aqueoussolution (e.g., shampoo). One way in which volatile solvents could becompletely or partially replaced would be to use a water-soluble productwhose affinity for hair exceeds its affinity for the aqueous solvent inwhich it is applied.

The principal component of hair is a protein called keratin. Threeimportant factors in determining the binding of a polymer to keratinare: (1) the affinity of the polymer for keratin, (2) the strength ofinteractions of the polymer with the solvent phase, and (3) thediffusibility of the polymer into the hair. Polymer-keratin affinity isinfluenced by polymer charge, molecular size, isoelectric point of thehair, pH of the surrounding medium, formulation composition, andsubstituents attached to the surface of the keratin. The hydrophilicityor hydrophobicity of the polymer affects binding interactions with theaqueous phase. Diffusion into the fiber is controlled by the molecularsize of the polymer, pH, reaction temperature, and the past history ofthe keratin (hysteresis).

Adsorption of a polymer onto keratin may be charge driven orhydrophobically driven. The adsorption process is a continuum betweenthese two pathways, and can vary with changes in the pH or in thepolymer structure. At low pH (pH<3.6), the adsorption of cationicpolymers is hydrophobically driven as the pH is near or below theisoelectric point of hair. As pH increases above 3.6, the adsorptionprocess becomes charge-driven as the negative charge of the hair fiberincreases with increasing pH.

Bonding between polymers and keratin falls into three principal types:primary valence bonds (both ionic and covalent), polar interactions(especially hydrogen bonding), and van der Waals attractions. Cationicpolymers in particular primarily bind to keratin through ionic bonds,enhanced by van der Waals forces. The strength of van der Waals bondingmay approach that of ionic bonding, as the sum of individual van derWaals interactions increases with the number of repeat units in thepolymer.

Polymeric quaternary ammonium salts ("polyquats") have been used forseveral purposes in cosmetic formulations due to their solubility inboth aqueous and aqueous-alcoholic media. Polyquats have been used asthickeners, emulsifiers, fixatives, film formers, and additives informulations to improve combing of hair, manageability, body, curlretention, and binding to keratin. Cationic ingredients tend to bind tohair keratin due to the low isoelectric point of hair (pH=3.67).

Prior polyquaternary ammonium cellulosic derivatives typically have alow degree of desorption from keratin, resulting in "buildup" or soilingof hair, and they can be resistant to removal by anionic surfactants.These problems have limited their use. Prior polyquaternary ammoniumcellulosic derivatives have had low solubility in water, requiring theuse of high levels of volatile organic compounds in many hairformulations. Current environmental regulations require the reduction ofvolatile organic compounds, making the long-term use of priorpolyquaternary ammonium cellulosic derivatives impractical for manyapplications.

Cellulose. Cellulose, a major component of most terrestrial plants, is apolymer formed of repeating β-1,4 D-glucose units ("anhydroglucoseunits."). Numerous hydroxyl groups on cellulose participate in extensiveintra- and inter-molecular hydrogen bonding, making cellulose a stiff,rod-like polymer. Reactions with cellulose generally require initialactivation of the hydroxyl groups to enhance nucleophilicity.

The applications and properties of cellulose derivatives are greatlyinfluenced by the degree of substitution along the cellulose chain. The"degree of substitution" is defined as the average number of hydroxylgroups that have been substituted per anhydroglucose unit in thepolymeric backbone. Each anhydroglucose unit has three hydroxyl groups,located at the C2, C3, C6 positions. The C2 and C3 positions aresecondary alcohols, and C6 is a primary alcohol. The three hydroxylgroups exhibit different rates of reactivity to different reagents. Inan etherification reaction, the order of reactivity is C2>C6>C3.

Cellulose ethers are generally soluble in water or common organicsolvents. They can be prepared by nucleophilic substitution reactionsunder alkaline conditions. The most important commercially availablecellulose ethers, such as carboxymethyl cellulose (CMC), methylcellulose(MC), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose (HPC)are prepared by this method. The Michael addition is used to preparecyanoethylated cellulose or carbamoyl cellulose by treating cellulosewith acrylonitrile or acrylamide, respectively. Cellulose ethers areused as thickeners, flow control agents, suspending agents, protectivecolloids, films, and thermoplastics. Cellulose ethers are generallynontoxic to humans, animals, and ecological systems.

Amino Cellulose Derivatives The introduction of amino groups ontocellulose molecules increases reactivity by forming a cellulosate"macroinitiator." that is suitable for further derivatisation. Aminocellulosics have been used as immunoadsorbents, in enzymeimmobilization, as ion-exchange resins, and as macroinitiators for vinylmonomers.

The preparation of primary aminoalkyl cellulosics generally involvesreacting activated cellulose with aminoalkyl halides, aminoalkylsulfuricacid, or ethylenimine. Another method to prepare aminoalkyl cellulosicsinvolves the direct reduction of the nitrile group of cyanoethylatedcellulose to give aminopropyl cellulose. The Hofmann rearrangement ofcarbamoylethylcellulose with Br₂ /NaOH for 30-120 min also givesaminopropyl cellulose. Reacting activated cellulose withepichlorohydrin, followed by subsequent reaction with various diaminesgives O-[2-Hydroxy-3-(ω(-aminoalkylamino) propyl cellulose. Celluloseacetate may be treated with sodium naphthalene in tetrahydrofuran toprepare the sodium cellulosate initiator. The sodium cellulosateinitiator can then react with the N-carboxy anhydride derivative of D,Lphenylalanine, γ-benzyl-L-glutamate, s-benzyl-L-cysteine, or sarcosineto yield single aminoacid cellulose derivatives, without formingpolypeptide graft copolymers.

Aminocarbamoyl Cellulosics. A water soluble 2-aminoethyl-carbamoylcellulose with a low degree substitution (DS≦0.02) may be prepared bytreating sodium carboxymethyl cellulose with excess ethylenediamine inthe presence of water soluble carbodiimides.

Converting carboxymethyl cellulose to an alkyl ester produces aderivative more receptive to aminolysis, thus increasing the degree ofsubstitution. For example, reacting carboxymethyl cellulose ("CMC")(DS>0.1) with methyl chloride at 100° C. yields methylcarboxymethylcellulose ester. Reacting this ester with various diaminesin methanol at 150° C. for 1 hour yields aminoamide cellulosics. Theaminoamide cellulosics may be quaternized by treatment withmethylchloride in methanol at room temperature. The quaternizedderivatives had a degree of substitution of 0.67. Betainized cellulosederivatives are prepared after treating the aminoamide cellulosics withCl(CH₂)_(y) CO₂ Na in isopropanol at 60° C. for 6 hours. The quaternizedand betainized cellulosics (DS=0.63) can be applied as hair bleaches andshampoos.

Hydroxyethylcellulose was treated with the betainization reagentprepared by heating a mixture of dimethylglycine, isopropanol, andepichlorohydrin at 50° C. The betainized cellulose improved the feel andcombing capacity of hair. The CMC ester may be prepared by treating theCMC salt (DS=1) with dimethylsulfate in isopropanol at 25° C. for 2hours and 70° C. for 2 hours. The CMC ester is treated with variousdiamines in toluene at 100° C. for 5 hours, giving aminoamides with a DSof 0.7. The quaternized derivatives have been used to flocculate chinaclay suspensions.

U.S. Pat. No. 4,988,806 discloses certain aminoalkylcarbamoylmethylcellulosics, certain monoquaternary ammoniumalkylcarbamoylmethylcellulosics, and their use in cosmetic preparations.

U.S. Pat. No. 4,415,552 discloses aminoalkylcarbamoylmethyl cellulosicssaid to be useful as non-immunogenic carriers for allergenic haptens, tohelp establish immunological tolerance to those haptens. See also Chem.Abstracts 97:203224b (1982).

D. Culberson et al., "Approaches to the Synthesis of AminoalkylcarbamoylCellulosics," Polym. Preprints, vol. 34, no. 1, pp. 564-565 (1993); andD. Culberson et al., "Synthesis and Characterization ofAminoalkylcarbamoyl Cellulosics," Polym. Mat. Sci., vol. 71, pp. 498-499(1994) disclose the synthesis and characterization of aminopropylamidocarboxyethyl cellulose, certain aminoalkyl carboxyamidomethylcelluloses, and certain poly quaternary ammonium salts.

D. Culberson et al., "A Study of the Complexation of Alkyl SulfateSurfactants with Aminoalkylcarbamoyl Cellulosics," printed abstract andcopy of slides given at oral presentation, Am. Chem. Soc. Meeting,Anaheim, CA (April 1995) discloses phase diagrams of mixtures of aqueoussurfactants with certain aminoalkylcarbamoyl cellulosics.

M. Manuszak-Guerrini et al., "A Study of the Complexation ofAminoalkylcarbamoyl Cellulosics and Oppositely Charged Mixed Micelles,"preprint of oral presentation, Society of Cosmetic Chemists NationalMeeting, New York, pp. 57-59 (December 1995) discloses measurements onthe interaction of certain aminoalkylcarbamoyl graft copolymers withsodium dodecyl sulfate-octoxynol mixed micelles. See also M.Manuszak-Guerrini et al., "Structure Elucidation of Complexes ofAminoalkylcarbamoyl Cellulosics and Oppositely Charged Mixed Micelles,"preprint of poster presentation submitted for Am. Chem. Soc. Mtg., NewOrleans, La. (Mar. 24-27, 1996).

D. Culberson, "Synthesis and Characterization of AminoalkylcarbamoylCellulosics," pp. 7-53, and 139-146, PhD Dissertation, Louisiana StateUniversity, Baton Rouge, La. (May 1995) discloses the synthesis andcharacterization of a number of aminoalkylcarbamoyl cellulosics.

Certain polysaccharide derivatives for use in hair, cosmetic, andflocculating compositions are disclosed in Chem. Abstracts 113:29109e(1989); Chem. Abstracts 112:160864u (1989); Chem. Abstracts 112:200955h(1989); and Chem. Abstracts 115:282370n (1991).

SUMMARY OF THE INVENTION

Novel water-soluble quaternary ammonium cellulosic derivatives ofcontrolled charge density have been discovered. These derivatives areuseful in cosmetic preparations, such as hair and skin formulations,particularly as hair conditioners.

These quaternized cellulosic derivatives are useful as thickeners,conditioners, film formers, fixatives, emulsifiers, or additives in hairor skin formulations to improve combing, manageability, body, curlretention, moisture resistance, and binding of ingredients to keratin.Compared to existing agents, the novel compounds have improvedtemperature stability, improved interactions with surfactants (such asin shampoos), improved binding to keratin, improved mechanicalproperties, and can mend split ends on hair. A major advantage of thenovel compounds is that they may be applied to hair directly from anaqueous solution, and do not require a volatile organic compound solventas carrier. Alternatively, smaller amounts of VOC's may be used than isthe case in current products, to improve drying times for theformulations.

The novel compounds are also useful as antistatic agents, bactericides,flocculating agents, and as drug binding or drug delivery agents.

A monoquaternary ammonium cellulosic derivative may be illustratedschematically as: ##STR1##

A diquaternary ammonium cellulosic derivative may be illustratedschematically as: ##STR2##

A polyquaternary ammonium cellulosic derivative may be illustratedschematically as: ##STR3##

More particularly, diquats in accordance with the present invention arederivatives of carboxymethyl cellulose in which some or all of thecarboxymethyl groups are replaced by diquaternary ammonium groups of thegeneral formula ##STR4## wherein there are at least about 0.2 suchdiquaternary ammonium groups present for each anhydroglucose unit of thepolymeric molecule, preferably between about 0.3 and about 0.7diquaternary groups per anhydroglucose unit, most preferably about 0.5;and wherein:

R¹ is hydrogen or methyl, preferably hydrogen.

R² is a divalent aliphatic hydrocarbon group with 2 to 20 carbon atoms,preferably --CH₂ --CH₂ -- or --CH₂ --CH₂ --CH₂ --.

R³, R⁴, R⁶, R⁷, and R⁸ are alkyl groups with 1 to 4 carbon atoms thatmay be the same as one another or different from one another, and arepreferably each methyl groups.

R⁵ is a substituted or unsubstituted divalent aliphatic group with 2 to5 carbon atoms, preferably --CH₂ --CH(OH)--CH₂ --.

X¹ and X² are anions that may be the same as one another or differentfrom one another; preferably a halide, a sulfate ester group, or asulfonic acid group, most preferably chloride.

Polyquats in accordance with the present invention are derivatives ofcarboxymethyl cellulose in which some or all of the carboxymethyl groupsare replaced by polyquaternary ammonium groups of the general formula##STR5## wherein there are at least about 0.2 such polyquaternaryammonium groups present for each anhydroglucose unit of the polymericmolecule, preferably between about 0.3 and about 0.7 diquaternary groupsper anhydroglucose unit, most preferably about 0.5; wherein b is between2 and 8, preferably 4 or 5; and wherein:

R¹ is hydrogen or methyl, preferably hydrogen.

R² is a divalent aliphatic hydrocarbon group with 2 to 20 carbon atoms,preferably --CH₂ --CH₂ -- or --CH₂ --CH₂ --CH₂ --.

R³, R⁴, R⁶, R⁷, and R⁸ are alkyl groups with 1 to 4 carbon atoms thatmay be the same as one another or different from one another, and arepreferably each methyl groups.

R⁵ is a substituted or unsubstituted divalent aliphatic group with 2 to5 carbon atoms, preferably --CH₂ --CH(OH)--CH₂ --.

X¹ and X² are anions that may be the same as one another or differentfrom one another; preferably a halide, a sulfate ester group, or asulfonic acid group, most preferably chloride.

Water soluble aminoamides were obtained, for example, by reacting methylcarboxymethyl cellulose with an excess of diamines, NH₂ (CH₂)_(x) NR'R",where x is typically 2 or 3, and R', R" are typically H or CH₃. Thesederivatives were then quaternized with iodomethane and a catalyticamount of iodine to obtain monoquaternary salts. Alternatively, theaminoamide cellulosics were treated with N-(3-chloro-2-hydroxypropyl)trimethyl ammonium chloride to yield diquaternary cellulosicderivatives. As another alternative, polyquaternary ammonium cellulosicswere prepared by reacting the aminoamides with epichlorohydrin anddimethylamine.

DESCRIPTION OF PREFERRED EMBODIMENTS

Synthesis of Aminoalkylcarbamoylmethyl Cellulosics ##STR6##

Sodium carboxymethyl cellulose was readily converted to awater-insoluble methyl carboxymethyl cellulose ("MCMC") by a directdisplacement reaction with dimethyl sulfate. The reaction has beenconducted both in neat dimethyl sulfate and in DMSO solution. In eithercase an insoluble ester, MCMC, was obtained. The MCMC reacts underhomogeneous conditions with neat diamines to produce water soluble CMCamides. See Table 1.

                  TABLE 1                                                         ______________________________________                                                                 MCMC,                                                Run       Diamine        (g)     Yield, g (%)                                 ______________________________________                                        CMCED     ethylene diamine                                                                             2.14    1.84 (86%)                                   CMCNNED   N,N-dimethyl-  2.05    1.98 (97%)                                             ethylene diamine                                                    CMC13DAP  1,3-diamino-propane                                                                          2.07    1.58 (76%)                                   CMCJ148   Jeffamine 148  1.03    0.81 (79%)                                   ______________________________________                                         The abbreviations used above are as follows:                                  CMCED = aminoethylcarbamoyl methyl cellulose                                  CMCNNED = N,Ndimethylaminoethylcarbamoyl methyl cellulose                     CMC13DAP = aminopropylcarbamoyl methyl cellulose                              CMCJ148 = carbamoylmethyl celluloseg-co-(polyoxyethylene)-amine          

The conversion of the CMC salt to aminoamides via methyl carboxymethylcellulose (MCMC) was confirmed by Fourier transform infraredspectroscopy ("FTIR"). The carbonyl absorption shifted from 1606 cm⁻¹(CMC) to 1746 cm⁻¹ (MCMC), and finally to 1596 cm⁻¹ (CMC amide). Theappearance of amide I and II bands at 1660 and 1578 cm⁻¹ confirmed theamid ation of the CMC ester. Analysis of the ¹ H NMR spectra showed thepresence of positional isomers, arising from amidation at the C2 and C6positions on the glucose ring. The anhydroglucose ring protons appearedas a broad peak, 3.254-4.50 ppm. The alkyl substituent protons appearedfrom 2.40-3.24 ppm. Analysis of the ¹³ C NMR spectra showed the presenceof the anhydroglucose ring carbons C1 and C6 at 105.0 ppm and 60.0 ppm,respectively, and the C2-C5 carbons overlapping from 70.0-85.0 ppm. Theamide carbonyl was also present at 177.0 ppm.

The degree of amidation, shown in Table 2, was determined using amodified ASTM method for carboxymethylcellulose (sodium salt), and byelemental analysis. The aminoamide derivatives were dried and refluxedin glacial acetic acid for 2.5 hrs and allowed to cool. The solutionswere titrated conductrimetrically with perchloric acid and dioxane. Theresidual salts of the aminoamide derivatives after titration withperchloric acid/dioxane were not water soluble, nor were the acetatesalts formed during reflux in acetic acid. However, the salts wereslightly soluble in DMSO/H₂ O. High degrees of substitution weregenerally obtained, except for decreased substitution withN,N'1,2-dimethylethylene diamine (CMCSED) (DS=0.35) and 1,2diaminopropane (DS=0.37), attributed to steric effects. The degree ofamidation calculated from elemental analysis was in close agreement tothe DS calculated by titration. In Table 2, the figures in parenthesesare calculated from the nitrogen content of the polymers based onelemental analysis.

                  TABLE 2                                                         ______________________________________                                        Degree of Amidation and Intrinsic Viscosity                                               DS         meq/g                                                  Derivatives (titration)                                                                              (titration)                                                                             η = η.sub.sp /c                      ______________________________________                                        CMCED       .49        1.68      3.95                                         CMCNNED     .56        1.77      2.37                                         CMC13DAP    .51        1.70      2.44                                         CMCJ148     .65        1.79                                                   CMCNNED     .57 (.51)  2.64 (3.26)                                                                             3.90                                         CMCNNDAP    .66 (.57)  2.81 (3.54)                                                                             1.08                                         ______________________________________                                         Abbreviations used above:                                                     CMCNNDAP = N,Ndimethylaminopropylcarbamoylmethyl cellulose                    MCMC = methyl carboxymethyl cellulose ester                              

Reactivity of the Amino Functional Group To confirm that the amino endgroups were accessible to further modification, cross-linking of theaminoamide derivatives in Table 2 with excess epichlorohydrin underheterogeneous conditions at 70° C. was performed. ##STR7## The aminofunctional group initiated a nucleophilic attack on the epichlorohydrin,and subsequent displacement of the chloride by the intermediate alkoxideion reformed the epoxide derivative at room temperature. The mixtureswere washed with acetone and dried under vacuum. The extent of reactionwas estimated by the weight of product isolated (Table 3).

                  TABLE 3                                                         ______________________________________                                        Reactivity of Amino Functional Group                                                            epichlorohydrin       yield                                 Derivatives                                                                            sample (g)                                                                             (ml)        conditions                                                                              (g)                                   ______________________________________                                        CMCED    0.1078   10          70° C., overnight                                                                .0958                                 CMCNNED  0.1285   10          70° C., overnight                                                                .1114                                 CMC13DAP 0.1750   10          70° C., overnight                                                                .1556                                 CMCNNDAP 0.1020   10          70° C., overnight                                                                .0866                                 ______________________________________                                    

The derivatives were placed in distilled water; no dissolution occurred.Upon addition of 1% or 5% NaOH, the aminoamides prepared fromN,N'-dimethylalkylenediamines dissolved over a period of three days atroom temperature. Dissolution occurred because a nucleophilic attack bythe hydroxide opened the epoxide ring, forming the diol product. ¹ H NMRconfirmed the ring-opening of the aminoamide epoxide intermediate to thering-opened diol aminoamide derivative. The aminoamides prepared fromthe unsubstituted diaminoalkanes formed predominantly cross-linkednetworks that were partially soluble under basic conditions. Thedifference in the reactivity of the amino functional groups was clearlyrelated to steric factors. The more sterically crowded tertiary aminoend groups stopped at the epoxide intermediate, whereas the lesshindered primary amino end groups formed the cross-linked networks.

Thermal Analysis. A differential scanning calorimetry trace of the MCMCester showed two transitions, a T_(M1), 90.3° C. and a Td (exothermic),300.1° C. (Table 4). Amidation lowered T_(M1), 90.3° C., by .sup.˜20-30° C. for the aminoamide cellulosics. The DSC traces showed apossible Tg at .sup.˜ 12° C., and the onset of the broad melttransition, T_(M1), at .sup.˜ 68° C. The shift to a lower T_(M1) wasattributed to side chain mobility. An additional transition, notobserved in MCMC ester, appeared at 207.8° C., 206° C., and 213.4° C.for the CMCNNED, CMC13DAP, and CMCNNDAP aminoamide cellulosics,respectively. This transition was attributed to the loss of the sidechain. The decomposition temperature T_(d) was only mildly effected byamidation. CMCNNED and CMCNNDAP showed a small increase in T_(d), whileCMCED and CMC13DAP showed a small decrease in T_(d). (All samples wereinitially heated to a 130° C. to remove any absorbed water.)

Typically, the temperature of onset of major weight loss for unmodifiedcellulose is between 270-300° C. In general, purification by bleachingand scouring raises this onset temperature, while chemical modificationssuch as tosylation, cyanoethylation, disulfide crosslinking,thioacetylation, benzhydrylation, and tritylation tend to lower thedecomposition temperature of cellulose.

                  TABLE 4                                                         ______________________________________                                        Comparison of the DSC Transitional Temperatures                               for Aminoalkylcarbamoylmethyl cellulosics                                     Derivatives  T.sub.M1                                                                             T.sub.M2 T    T.sub.d (exo).sup.a                         ______________________________________                                        MCMC         90.3            233.3                                                                              300.1                                       CMCED        59.6            253.9                                                                              287.5                                       CMCNNED      79.1   207.8    262.9                                                                              307.1                                       CMC13DAP     81.9   206.4    263.1                                                                              293.1                                       CMCNNDAP     68.0   213.4    261.3                                                                              302.9                                       ______________________________________                                         (a) Exothermic decomposition temperature.                                

The modified celluloses, CMC salt and MCMC ester, showed a decrease inthe onset of thermal decomposition at 264.4° C. and 244° C. C.(T_(d2))respectively (Table 5). Interestingly, the amidation of the MCMC esterincreased the thermal stability of the modified cellulose to a thermaldecomposition temperature slightly higher than that of CMC salt. For theaminoamide cellulosic TGA traces, the first observable weight loss forthe aminoamide cellulosics occurred between 264.4° C. and 271.9° C.(T_(d2)); weight loss then accelerated to an inflection point near293.9-305.5° C. (T_(d3)), and leveled off between 316.0° C. and 333.7°C. (T_(d4)). The DTA traces did show an endotherm associated with theformation and volatilization of levoglucosan at 278.2° C. (CMC), 307.6°C. (MCMC), 295.0° C (CMCNNDAP), 299.2° C. (CMCNNED), and 286.6° C.(CMCED and CMC13DAP). The aminoamides containing primary amino endgroups on their side chains, CMCED and CMC13DAP, showed an initialweight loss, T_(d1), that was not observed for the starting materials,CMC salt and MCMC, or for CMCNNED and CMCNNDAP. This initial weight losswas attributed to "bound" water that was tightly held through hydrogenbonding with the primary amino groups, and that was not driven off bythe initial heating to 130° C.

                  TABLE 5                                                         ______________________________________                                        Comparison of TGA Decomposition Temperatures                                  of Aminoalkylcarbamoylmethyl cellulosics                                                                              char at                               Derivatives                                                                             T.sub.d1 T.sub.d2                                                                              T.sub.d3                                                                            T.sub.d4                                                                             500° C.                        ______________________________________                                        CMC                264.4   276.1 288.3  39.1%                                                    (11.3%) (25.5%)                                                                             (51.5%)                                      MCMC               244.5   301.3 345.8  33.0%                                                    (14.1%) (37.6%)                                                                             (58.9%)                                      CMCED     132.1    268.2   293.9 316.0  27.4%                                           (10.2%)  (18.0%) (42.7%)                                                                             (60.8%)                                      CMCNNED            271.9   305.5 336.0  16.4%                                                    (15.2%) (47.2%)                                                                             (76.1%)                                      CMC13DAP  168.8    265.3   295.0 323.0  19.7%                                           (11.6%)  (19.7%) (44.7%)                                                                             (66.2%)                                      CMCNNDAP           265.3   304.5 333.7  16.3%                                                    (14.6%) (48.6%)                                                                             (74.4%)                                      ______________________________________                                         (1) The percentages in parentheses denote percentage loss of material at      that temperature.                                                             (2) The char percentage is the amount of char remaining at 500° C.

Synthesis of Cationic Cellulosic Quaternary Ammonium Salts("Monoquats"). The quarternary ammonium salts ("monoquats") were readilyprepared from the aminoamide derivatives by slurrying in iodomethanewith a small amount of iodine catalyst at room temperature for 3 days(Table 6). The aminoamides were purified by washing in acetone anddrying under vacuum. ##STR8##

The discovery that iodine catalyzes the above reaction wasserendipitous. This reaction was originally performed with iodomethanefrom an older jar of that reagent, without intentionally added catalyst.The reaction proceeded as depicted above. But when the reaction wasrepeated with reagent taken from a newer jar of iodomethane, thereaction did not occur. Investigation revealed that the difference wasthat the "old" iodomethane incorporated a small amount of elementaliodine as a breakdown product, while the "new" iodomethane did not.Adding a small amount of I₂ to the "new" CH₃ I caused the reaction toproceed successfully.

                  TABLE 6                                                         ______________________________________                                        Preparation of Monoquats                                                      Derivatives    sample (g)                                                                             yield (g)                                             ______________________________________                                        MQNNED         1.03     1.10                                                  MQ13DAP        0.42     0.54                                                  MQNNDAP        1.02     1.10                                                  ______________________________________                                         Abbreviations used above:                                                     MQNNED = trimethylammonium methyl carbamoylmethyl cellulose chloride          MQ13DAP = trimethylammonium propyl carbamoylmethyl cellulose chloride         MQNNDAP = methylammonium propyl carbamoylmethyl cellulose chloride       

Resulting cationic charge densities are shown in Table 13 below. Thehydrogen chloride derivatives of the aminoamides were prepared bystrongly acidifying the solutions prior to titration with potassiumpolyvinylsulfate, (PVSK) (Table 10 below).

Synthesis of Diquaternary Ammonium Salts ("Diquats"). The quaternizingagent Quat 188 (Dow Chemical) is a 65% aqueous solution ofN(-3-chloro-2-hydroxypropyl) trimethylammonium chloride: ##STR9##

The quaternization of the aminoamide cellulosics occurs through the morereactive epoxidized Quat 188. The epoxidized derivative is formed insitu upon addition of NaOH: ##STR10##

In this synthetic scheme, note that the value of "x" may readily bemanipulated to alter the extension of the side groups attached from thecellulosic backbone. A preferred value for "x" is 2 or 3.

The aminoamide cellulosics were dissolved in 1% NaOH (Table 7) or 10%NaOH (Table 8), and then 10 ml of Quat 188 1.15 was added. The solutionswere allowed to react for 4 days at room temperature, dialyzed for 3days against distilled, deionized water, and then freeze-dried. The NaOHsolution (1% or 10%), was used both as a solvent for the aminoamides,and as a reagent to epoxidize the Quat 188. The amino functional groupattacked the epoxidized Quat 188 to form the diquats. Analysis of the ¹H NMR confirmed the addition of Quat 188 to the aminoamide cellulosics.

                  TABLE 7                                                         ______________________________________                                        Preparation of Diquats with 1% NaOH                                                                       NaOH (1%)                                         derivatives                                                                           sample (g) Q188 (ml)                                                                              (ml)      yield (g)                               ______________________________________                                        DQED    0.1072     10.0     10.0      0.1611                                  DQNNED  0.2655     10.0     10.0      0.2872                                  DQ13DAP 0.1767     10.0     10.0      0.2048                                  DQNNDAP 0.1060     10.0     10.0      0.1374                                  ______________________________________                                         Abbreviations used above:                                                     DQED = trimethylammonium2-hydroxypropyl-N-ammoniumethyl carbamoylmethyl       cellulose chloride                                                            DQNNED = trimethylammonium2-hydroxypropyl-N,N-dimethylammoniumethyl           carbamoylmethyl cellulose chloride                                            DQ13DAP = trimethylammonium2-hydroxypropyl-ammoniumpropyl carbamoylmethyl     cellulose chloride                                                            DQNNDAP = trimethylammonium2-hydroxypropyl-N,N-dimethylammoniumpropyl         carbamoylmethyl cellulose chloride                                       

                  TABLE 8                                                         ______________________________________                                        Preparation of Diquats with 10% NaOH                                                                      NaOH (10%)                                        derivative                                                                            sample (g) Q188 (ml)                                                                              (ml)      yield (g)                               ______________________________________                                        DQNNED  2.01       10.0     10.0      2.33                                    DQ13DAP 0.63       10.0     10.0      0.79                                    DQNNDAP 0.80       10.0     10.0      0.54                                    ______________________________________                                    

Synthesis of Polyquaternary Ammonium Salts (Polyquats). Polyquaternaryammonium salt copolymers were prepared by reacting aminoamidecellulosics with epichlorohydrin and dimethylamine as shown (Table 9):##STR11##

As for the diquats, the value of "x" may readily be manipulated to alterthe size of the side chains. The value of "b" may also readily bemanipulated to alter the charge density. Typical values of "b" are 4 or5.

The aminoamides cellulosics CMCNNED and CMCNNDAP have tertiary aminoterminal groups on the side chains. The nucleophilic attack of thetertiary amino groups on epichlorohydrin gave an intermediate containinga quaternary ammonium salt and an a epoxide. The more reactivedimethylamine could then attack the epoxide, opening the ring, thuscontinuing the nucleophilic addition of the epichlorohydrin anddimethylamine. Analysis of the ¹ H NMR showed broad overlapping peaks. Acomparison of ¹³ C NMR analysis of the starting aminoamide cellulosicsto the polyquat showed additional carbon signals in the all region ofthe spectra, corresponding to the quaternized derivative.

                  TABLE 9                                                         ______________________________________                                        Preparation of Polyquats                                                              sample  dimethyl- epichlorohydrin                                                                              yield                                Derivatives                                                                           (g)     amine (ml)                                                                              (ml)     time  (g)                                  ______________________________________                                        PQNNED.sup.a                                                                          0.4396  10.0       1.0     1 day 0.9733                               PQNNDAP.sup.b                                                                         0.5356  25.0      15.0     3 days                                                                              1.4063                               PQNNED.sup.a                                                                          0.6100  10.0       5.0     1 hr.                                      PQNNDAP.sup.b                                                                         0.1840  16.0      17.0     3 days                                                                              1.5747                               ______________________________________                                         .sup.(a) The product was precipitated in acetone and dried under vacuum.      .sup.(b) The product was dialyzed and freezedried.                            Abbreviations used above:                                                     PQNNDAP = N,Ndimethylammoniumpropyl carbamoylmethylcelluloseg-co              (polyN3-trimethylammonium-2-hydroxypropyl) chloride                           PQNNED = N,Ndimethylammoniumethyl carbamoylmethyl celluloseg-co               (polyN3-trimethylammonium-2-hydroxypropyl) chloride                      

Determination of Cationic Charge Density. In conventional analyses ofpolyelectrolytes, the anionic or cationic colloid is typically titratedwith either polydiallyldimethylammonium chloride (DADMAC) or potassiumpolyvinylsulfate (PVSK), respectively. The endpoint is determined by thecolor change of toluidine blue indicator from blue to red-wine.Conductimetric, turbidimetric, and iodine ion selective electrodemethods have also been used to analyze polyelectrolytes. More recentmethods for determining charge density include fluorescent indicatorssuch as 6-(p-toluidino)-2-naphthalenesulfonic acid, potassium salt(TNS); 8-anilino-1-naphthalenesulfonic, ammonium salt (ANS); acridineorange; acriflavine hydrochloride; and safranine O to directly titrateanionic and cationic polyelectrolytes with 10⁻⁴ standard solutions ofDADMAC and PVSK. The unbound dyes are practically nonfluorescent butexhibit strong fluorescence when bound to a polyelectrolyte. Thefluorescence intensity of the polyelectrolyte-dye complex diminisheswhen titrated with a standard solution of PVSK or DADMAC. During thetitration with PVSK or DADMAC the dye is liberated and is substitutedwith the PVSK or DADMAC. The fluorescence intensity becomes constantafter the endpoint is reached.

The aminoamide derivatives were quaternized to different degrees ofquaternization: mono., di-, and poly-quaternization. Turbidimetric andindicator methods proved to be most effective in analyzing thequaternized aminoamide cellulosics. Sodium dodecyl sulfate (SDS) andPVSK were standardized with cetylpyridinium chloride monohydrate (CPM).The quaternized cellulosics were dissolved in distilled water. Aliquotsof the solutions were titrated using PVSK or SDS with continuousstirring and pH monitoring. The pH was adjusted as needed with HCl orNaOH solutions. The turbidity and indicator methods were performedsimultaneously by adding 2 drops of toluidine blue indicator to thesample. Aliquots of the sample were pipetted into cuvettes, and theturbidity was monitored as percent transmittance. A titration curve oftransmittance vs. volume of titrant was plotted, and the endpoint wasdetermined as the inflection point. The indicator color changed fromblue to red-wine. An initial reduction in transmittance at 600 nm wasobserved due to the presence of the indicator. A reduction intransmittance at 520 nm increased in intensity as the observedequivalence point was detected by the color change. However, thetoluidine blue indicator was not effective for titrations using SDS: Atthe presumed equivalence point there was no color change. However, thesolutions did become turbid, and the turbidity method was suitable forturbidimetric analysis of the polyelectrolytes.

The cellulosic aminoamides were treated with HCl at room temperature toyield cellulosic ammonium amide hydrogen chlorides. The pH (2.5) wasmaintained by adjustment with HCl and NaOH as needed. The charge pergram (meq/g), determined by the turbidimetric method, was approximatelyhalf that determined by the conductimetric method (Table 10). Thediscrepancy in the measurements was attributed to two factors: (1)titrant diffusion through the media, and (2) quaternization of the aminoend group. In the conductimetric method, the cellulosic aminoamides wererefluxed in acetic acid to quaternize the amino moiety, whereasquaternization with HCl at room temperature was used for the turbiditymethod. Both techniques relied on diffusion of the titrant to complexwith the poly-ion. Perchloric acid was the titrant in the conductimetricmethod, which involved complexation with the acetate ion. The turbiditymethod required the complexation of two polymers (PVSK and titrant) withthe charged cellulosic aminoamide for precipitation to occur.

The diquats (1% NaOH) were analyzed with both the toluidine blueindicator and the turbidity method. The diquats were dissolved indistilled water, and 2 drops of indicator were added. The derivativeswere titrated with PVSK to the indicator endpoint, blue to red-wine.Hydrochloric acid was added and the pH adjusted to 2.5. The titrationwas continued with the PVSK to the turbidimetric endpoint. The extent ofquaternization for the diquats prepared with 1% NaOH was less than 0.1for all the derivatives (Table 11). Upon acidification, the unreactedamino groups were quaternized and the extent of quaternization was thenclose to that of the cellulosic ammonium amide hydrochlorides (Table12).

The quaternization of diquats prepared with 10% NaOH was also determinedby the indicator and turbidity methods. The concentration of baseaffected the extent of quaternization substantially. Compare Table 11with Table 14.

                  TABLE 10                                                        ______________________________________                                        Turbidimetric Titration of Monoquat Hydrogen chlorides                        Derivatives                                                                             mg of sample  ml of PVSK                                                                              meq/g                                       ______________________________________                                        MQED      4.13          23.0      1.15                                        MQNNED    6.20          19.5      0.65                                        MQ13DAP   2.76          11.0      0.82                                        MQNNDAP   4.34          15.5      0.74                                        ______________________________________                                         N = 2.06 × 10.sup.-.sup.4 eq/l; pH = 2.5                           

                  TABLE 11                                                        ______________________________________                                        Determination of Cationic Charge for Diquats* at pH = 6.0                     Derivatives                                                                            mg of sample                                                                              ml of PVSK meq/g (Indicator)                             ______________________________________                                        DQED     3.72        0.4        0.022                                         DQNNED   3.67        1.2        0.067                                         DQ13DAP  3.99        0.9        0.046                                         DQNNDAP  3.61        1.4        0.080                                         ______________________________________                                         (1) N = 2.06 × 10.sup.-.sup.4 eq/l; pH = 6.0                            (2)* Diquats prepared with 1% NaOH.                                      

                  TABLE 12                                                        ______________________________________                                        Determination of Cationic Charge for Diquats at pH = 2.5                                       ml of    ml of                                                        mg of   PVSK     PVSK   meq/g  meq/g                                 Derivatives                                                                            Sample  (turbidity)                                                                            (Indicator)                                                                          (turbidity)                                                                          (indicator)                           ______________________________________                                        DQED     3.72    12.0     11.5   0.66   0.64                                  DQNNED   3.67    14.5     16.3   0.66   0.91                                  DQ13DAP  3.99    15.0     14.0   0.81   0.72                                  DQNNDAP  3.61    12.5     10.0   0.72   0.57                                  ______________________________________                                         (1) N = 2.06 × 10.sup.-4 eq/l; pH = 2.5                                 (2) Diquats prepared with 1% NaOH                                        

For the polyquaternary ammonium cellulosics, titrating with PVSK provedto be effective. However, when analyzing the graft polycationiccellulosic, monoquats, and diquats, the use of sodium dodecyl sulfate("SDS"), a twelve carbon anionic surfactant, was more effective foranalyzing short chains grafts. After the less-bully SDS complexed withthe first charge, the second charge was still accessible. Analysis ofthe cationic charge density for the graft polycationic cellulosics withSDS as titrant showed an average of one charge for the monoquats (Table13), two charges for the diquats (Table 14), and five charges for thepolyquats (Table 15). Analysis of the charge density with PVSK showed ageneral increase with quaternization for the monoquats and diquats, butwas in close agreement with that of the polyquats. The agreement ofcharge density with the PVSK and SDS titrations for the polyquatssuggested that the length of the cationic graft did influence theeffectiveness of the polymer-polymer titration.

                  TABLE 13                                                        ______________________________________                                        Cationic Charge Density of Monoquats                                                  SDS (meq/g)  PVSK (meq/g)                                                                             PVSK (meq/g)                                  monoquats                                                                             (turbidity)  (turbidity)                                                                              (indicator)                                   ______________________________________                                        MQNNED  0.97         0.11       0.11                                          MQ13DAP --           0.25       0.31                                          MQNNDAP 1.26         0.40       0.38                                          ______________________________________                                         SDS: N = 2.03 × 10.sup.-3 eq/l: PVSK: N = 2.24 × 10.sup.-4        eq/l (turbidity)                                                              PVSK: N = 1.49 × 10.sup.-4 eq/l (indicator)                        

                  TABLE 14                                                        ______________________________________                                        Cationic Charge Density of Diquats*                                                                PVSK (meq/g)                                                                             PVSK (meq/g)                                  Diquats SDS (meq/g)  (turbidity)                                                                              (Indicator)                                   ______________________________________                                        DQNNED  1.96         0.94       0.67                                          DQ13DAP 2.13         0.97       0.79                                          DQNNDAP 1.74         0.69       0.56                                          ______________________________________                                         (1) SDS: N = 2.03 × 10.sup.-3 eq/l: PVSK: N = 2.24 × 10.sup.-     eq/l (turbidity)                                                              PVSK: N = 1.49 × 10.sup.-4 eq/l (indicator)                             (2)* Diquats prepared from 10% NaOH.                                     

                  TABLE 15                                                        ______________________________________                                        Cationic Charge Density of Polyquats                                                    SDS       PVSK (meq/g)                                                                             PVSK (meq/g)                                   Derivatives                                                                             meq/g     Turbidity  Indicator                                      ______________________________________                                        PQNNED              3.84       4.68                                           PQNNDAP   4.44      4.40       3.75                                           PQNNED    2.72      0.82       0.94                                           PQNNDAP   5.35      6.47       4.31                                           ______________________________________                                         SDS: N = 2.03 × 10.sup.-3 eq/l: PVSK: N = 2.24 × 10.sup.-4        eq/l (turbidity)                                                              PVSK: N = 1.49 × 10.sup.-4 eq/l (indicator)                        

Viscosity. The diquats of the present invention have superior viscosityeffects when compared to those of otherwise comparable monoquats, makingthem very useful in hair care gels, shampoos, conditioners, mousses, andthe like in which a high viscosity is desired. For example, whendissolved in water alone at 25° C., a solution of the diquat DQNNED hada viscosity about 15 times higher than that of a solution of themonoquat MQNNED. When 10% to 50% ethanol was added to these aqueoussolutions, the viscosity of the DQNNED solution changed little, whilethe viscosity of the MQNNED solution dropped to about one-third of itsoriginal value, or about 50 times lower than the viscosity of theaqueous alcohol solution of DQNNED.

Thus the novel diquats allow good rheological control of hair care andother cosmetic formulations, while using less polymer and less VOC's.

Bactericidal Properties. The novel polymers also have advantageousbactericidal properties. Samples of the polymer DQNNED were tested forbactericidal activity against E. coli. A measured amount of the initialinoculum of bacteria plated about 980,000 colonies, taken at themidpoint of the bacterial growth phase to insure that the E. coli werereproducing at or near their maximal rate. The polymer DQNNED was addedto the medium to achieve a final concentration of 0.01 gram polymer per100 mL of solution. The bacteria were incubated at 25° C. for 2 hourswith the polymer, and were then plated. The same measured amount ofinoculum then plated only about 60,000 colonies, a substantial reductionin bacterial count equivalent to a two-hour logarithmic (base 10)reduction rate of about 1.2 for E. coli. Samples plated at times muchgreater than 2 hours gave colony counts too low to measure accurately.

Experimental Procedures--General

Elemental analyses were conducted by Oneida Research Services, Inc.(Whitesboro, N.Y.). Nuclear Magnetic Resonance (NMR) analyses wereperformed using Bruker (San Jose, Calif.) AC100, 200AC and AM400 NMRinstruments for ¹ H and ¹³ C NMR. Seiko Instruments (Torrance, Calif.)DSC220C, TG/DTA 220, and DMS200 instruments were used to analyze thethermal properties of the derivatives. Infrared spectra were obtainedwith a Perkin Elmer (Norwalk, Conn.) 1700X series Fourier transforminfrared (FTIR) spectrometer at 4 cm⁻¹ resolution and 10 to 25 scans.Intrinsic viscosities were measured in distilled water by standardprocedures using a Ubbelohde dilution viscometer. Cone/plate viscositieswere measured with a Brookfield Viscometer, CP #40. A UV-VIS-NIRScanning Spectrometer was used to measure % transmittance and UVabsorbance. A Spex (Edison, N.J.) Fluorescence Spectrometer was used toanalyze fluorescence intensities. A Virtis-Freeze (Gardiner, N.Y.)Mobile 12XL was used for lyophilization. A Radiometer (Copenhagen,Denmark) PHM82, standard pH meter equipped with a combination electrodewas used to monitor pH and conductivity.

Reagents and Solvents. Quat 188, 65% solution, was provided by DowChemical Company (Midland, Mich.).

All other reagents: cetylpyridinium chloride monohydrate (CPM);potassium polyvinylsulfate (PVSK); cyanoethylated cellulose (CEC);6-(p-toluidino)-2-naphthalenesulfonic acid, potassium salt (TNS);8-anilino-1-naphthalenesulfonic, ammonium salt (ANS); ethylene diamine;N,N-dimethylethylenediamine; 1,3-diaminopropane;N,N-dimethyldiaminopropane; N,N'-1,2-dimethylethylene diamine;1,2diaminopropane; and iodomethane were purchased from Aldrich(Milwaukee, Wis.). These reagents were used without furtherpurification.

Sodium dodecyl sulfate, 99% (SDS) was purchased from Sigma Chemical Co.(St. Louis, Mo.), and was used without further purification. Spectra/Pordialysis tubing, Spectrum Medical Industries Houston, Tex.) with amolecular weight cut off of 6,000-8,000 was used for lyophilization.

Preparation of Methyl Carboxymethyl Cellulose (MCMC). Commerciallyobtained sodium carboxymethylcellulose (10.35 g) was slurried in 20 mlof dimethyl sulfate for 1 day at room temperature. The crude reactionmixture was filtered, washed with copious amounts of water and methanol,and dried under vacuum. The MCMC ester (8.60 g, 83% conversion) was usedwithout further purification in subsequent syntheses. ¹ H NMR (D₂ O), δ(ppm): 3.1-4.4 (broad, overlapping peaks).

Preparation of Aminoalkylcarbamoylmethyl Cellulosics, Method One. Methylcarboxymethyl cellulose (1.10 g) was dissolved in excess RNH(CH₂)XNR'R"(20 ml) where R, R', R"═H or CH₃ ; and 0.2 g NH₄ Cl was added. Thereaction temperature was maintained at 90-100° C. for 1-5 hrs. Thereaction mixture was cooled and dialyzed for 3 days against distilledwater that was changed daily. The viscous crude mixture wasfreeze-dried. The product was redissolved in water, centrifuged, andrelyophylized.

¹ H NMR (D₂ O) δ (ppm): 3.25-4.50 (broad peaks of anhydroglucose ring);CMCED δ: 2.95 (s), 3.05 (t), 3.30 (t); CMCNNED .5: 2.45 (s), 2.75(overlapping triplets); CMC13DAP δ: 2.50 (p), 2.75 (t), 2.85 (t), 3.10(t); CMCNNDAP δ: 2.50 (p), 2.70 (s), 2.60 (t), 2.75 (t), 2.85 (t), and3.10 (t).

¹³ C NMR (D₂ O) δ (ppm): 70-85 (C2, C3, C4, and C5 of anhydroglucosering); CMCED δ: 104.6 (C1 of anhydroglucose ring), 54.6 (C6 ofanhydroglucose ring), 45.6, 40.9, 37.5, carbonyl (unobserved); CMCNNEDδ: 102.5 (C1 of anhydroglucose ring), 60.1 (C6 of anhydroglucose ring),56.7, 56.1 ,43.6 ,43.2 ,35.9 ,34.4; 177.9 (amide carbonyl); CMC13DAP .6:105.0 (C1 of anhydroglucose ring), 63.1 (C6 of anhydroglucose ring),40.9, 37.4, 180.8 (carbonyl); CMCNNDAP 6: 102.5 (C1 of anhydroglucosering), 56.2 (C6 of anhydroglucose ring), 43.9, 39.0, 38.3, 29.6, 25.3,15.1, 177.8 (amide carbonyl).

FTIR (cm⁻¹), KBr pellets: CMCED, 3413 (s, O--H stretch), 2928 (w, C--Hstretch), 1650 (amide I band, shoulder), 1592 (s, amide II band), 1125and 1061 (vs, C--O--C stretch); CMCNNED, 3436 (s, O--H stretch), 2923(w, C--H stretch), 1651 (amide I band, shoulder), 1593 (s, amide IIband), 1113 and 1061 (s, C--O--C stretch); CMC13DAP, 3410 (s, O--Hstretch), 2926 (w, C--H stretch), 1650 (amide I band, shoulder), 1591(s, amide II band), 1112 and 1060 (s, C--O--C stretch); CMCNNDAP, 3195(bs, O--H stretch), 2943 (w, C--H stretch), 1641 (s, amide band), 1058(s, C--O--C stretch).

The degrees of substitution of the salt and the aminoamide cellulosicswere determined by refluxing the dried derivatives in glacial aceticacid and conductrimetrically titrating with 0.1 N perchloricacid/dioxane solution. The degrees of substitution and the intrinsicviscosities were as follows: CMC (DS=0.70), CMCED (DS=0.63, meq/g=3.07,η=1.56), CMCNNED (DS=0.57, meq/g=2.64, η=3.90), CMCNNDAP (DS=0.66,meq/g=2.81, η=1.08), CMC12DAP (DS=0.37, meq/g=2.02) and CMCSED (DS=0.35,meq/g=1.88). Elemental analysis: CMCNNED, Calculated 41.27% C; 4.65% N;Found 43.14% C; 4.57% N; CMCNNDAP, Calculated 43.25% C; 4.93% N; Found44.09% C; 4.47% N.

Preparation of Aminoalkylcarbamoylmethyl Cellulosics, Method Two. TheMCMC was slurried in diamine, RNH(CH₂)_(x) NR'R", where R, R', R"=--H or--CH₃, and x=2 or 3, and this slurry was premixed for 3 days at roomtemperature. The reaction mixtures were then reacted at 90° C. for 1-3days. The products were purified by dialysis for three days againstdistilled water, which was changed daily. Any undissolved particulateswere removed by filtration. The filtered solutions were freeze-dried.The degrees of substitution of the CMC salt and of the aminoamidecellulosics were determined by refluxing the dried derivatives inglacial acetic acid and conductrimetrically titrating with 0.1 Nperchloric acid/dioxane solution.

Reaction of Aminoamide Cellulosics with Epichlorohydrin (EPC). Theaminoamides CMCED, CMCNNED, CMC13DAP, and CMCNNDAP, were separatelyslurried in 10 ml of EPC at 70° C. overnight. The reaction mixtures werecooled to room temperature, and washed with copious amounts of acetone.The products were dried overnight under vacuum. The solubilities of thederivatives were tested in distilled water and 1% NaOH. None of thederivatives was soluble in distilled water. The derivatives preparedfrom CMCNNED and CMCNNDAP dissolved in 1% NaOH after 3 days at roomtemperature.

¹ H (D₂ O) NMR δ (ppm): CMCNNED, 3.2-4.5 (broad, overlapping peaks ofanhydroglucose ring); 3.0-3.5 (m, overlapping); 2.5-2.2 (t, toverlapping); 2.0 (t), 1.7 (s). CMCNNDAP, 3.2-4.5 (broad, overlappingpeaks of anhydroglucose ring); 3.0 (t, overlapping peaks); 2.4 (t,overlapping peaks); 2.4 (s), 2.1 (s), 1.4 (m, broad).

Standardization of Perchloric Acid/Dioxane.

The titrant solution (0.1 N perchloric acid/dioxane) was prepared byadding 9 ml of perchloric acid to 1000 ml dioxane, and was stored in abrown bottle. A stock solution of potassium hydrogen phthalate ("KHP")was prepared by dissolving 2.5452 g KHP (dried at 120° C. overnight) in250 ml glacial acetic acid. A 10 ml aliquot of this solution was placedin a 500 ml beaker with an additional 50 ml of glacial acetic acid.Titrations were carried out with continuous stirring, and themillivoltage was monitored with a combination electrode connected to apH meter.

Determining the Degree of Substitution. The CMC salt, MCMC ester, andaminoamide cellulosics were separately dried at 110° C. for 2 days. Thedried derivatives were suspended in 75 ml glacial acetic acid in a roundbottom flask equipped with a stir bar and a water cooled condenser, andrefluxed for 2.5 hours. The solutions were then poured into a 400 mlbeaker with an additional 50 ml glacial acetic acid. The beaker wasequipped with a stir bar and combination electrode. The solutions weretitrated with 0.1N perchloric acid/dioxane solution with continuousstirring. The change in millivoltage was recorded from the pH meter.

Preparation of Quaternary Ammonium Salts. To a 25 ml or 50 ml roundbottom flask equipped with a magnetic stir bar, aminoamide cellulosics(Method 2) were slurried in iodomethane. The solutions were continuouslystirred for three days at room temperature. The products were purifiedby washing with copious amounts of acetone, and drying overnight in avacuum oven. The dried products were yellow and water soluble. Thedegree of substitution was determined by titrating with SDS and PVSK.

Preparation of Diquaternary Ammonium Salts. The aminoamide cellulosicswere dissolved in 10 ml of a 1% or 10% NaOH solution in a 25 ml or 50 mlround bottom flask equipped with a magnetic stirrer. Upon dissolution,10 ml of Quat 188 was added to the reaction mixture, and the reactionwas continued for 3 days at room temperature. The solutions weredialyzed for 3-5 days against distilled water, which was changed daily.The purified solutions were lyophilized. The degree of substitution wasdetermined by titrating with SDS and PVSK.

¹ H NMR (D₂ O), δ (ppm): 3.25-4.5 (anhydroglucose ring, broad,overlapping peaks); DQED, 4.5 (m, broad), 3.6 (d), 3.5 (d,soverlapping), 3.2 (s,s); DQNNED, 4.5 (.mn, broad), 3.6 (d), 3.5-3.4 (d,soverlapping), 3.1 (s), 2.9 (s). DQ13DAP, 4.5 (m, broad), 3.6 (d), 3.5(d,s overlapping), 3.4 (s, three), 1.9 (broad peak), DQNNDAP, 4.5 (m,broad), 3.6 (d), 3.4-3.5 (d,s overlapping), 3.3 (s), 3.2 (s), 3.1 (s),2.8 (s, two), 1.9 (broad peak).

Preparation of Polyquaternary Ammonium Salts. CMCNNED (0.4396 g) wasdissolved in 10 ml of dimethylamine (DMA), and 1.0 ml of epichlorohydrin(EPC) was then added dropwise in a three-neck round bottom flaskequipped with a magnetic stir bar, thermometer, and reflux condenser.Upon addition of EPC, the temperature of the reaction rose initially to50° C., but then dropped to 28° C. The mixture reacted overnight; theresultant viscous yellow solution was precipitated in acetone and driedunder vacuum. The final product, PQNNED (0.9733 g) was gelatinous inappearance.

¹ H NMR (D₂ O) δ (ppm): 3.25-4.5 (broad, overlapping peaks ofanhydroglucose ring), 3.5 (m, broad), 3.3-3.2 (d,d, broad, overlapping),2.9-2.8 (d), 2.6 (s). ¹³ C NMR (D₂ O) δ (ppm): 70-85 (C2-C6,anhydroglucose ring), 105.1 (C1), 70.3, 69.3, 63.5, 62.1, 59.4, 56.2,55.4, 45.9, 37.4, 176.0 (amide carbonyl). Elemental analysis of PQNNED:Calculated 35.81% C, 10.58% N; 21.57% Cl; Found 35.74% C, 10.56% N,22.62% Cl.

CMCNNED (0.6100 g) was dissolved in 10 ml of dimethylamine (DMA) in a3-neck, round bottom flask, equipped with a magnetic stir bar,water-cooled condenser, and thermometer. After the temperature droppedfrom 50° C., EPC (5 ml) was added, and the temperature rose to 100° C.After a few minutes the temperature dropped and the reaction mixturebecame gelatinous. After an hour, 50 ml of water was added and theproduct, PQNNED, was precipitated in copious amounts of acetone, anddried under vacuum.

CMCNNDAP (0.5356 g) was dissolved in 10.0 ml of dimethylamine ("DMA")and 5 ml of EPC in a three-neck round bottom flask equipped with amagnetic stir bar, thermometer, and reflux condenser. Upon addition ofEPC, the temperature rose to 60° C., and the solution became veryviscous. An additional 10 ml of DMA and 5 ml of EPC were added, and thereaction was allowed to proceed for 2 days. On day three, 5 ml of DMAwas added, and the reaction was continued at room temperature. On dayfour, the product was purified by dialysis against distilled water forthree days, and was then lyophilized. The final yield was 1.4063 g ofproduct, PQNNDAP. ¹ H NMR (D₂ O), δ (ppm): 3.2-4.5 (broad, overlappingpeaks of anhydroglucose ring); 4.9 (m, broad, NH); 3.1-3.6 (d,d,s,broad, overlapping); 2.4-2.3 (m), 2.2 (s), 1.5. 13C NMR (D₂ O), δ ppm):anhydroglucose ring (unobserved); 69.6, 64.3, 55.7 (m, broad); 47.3,165.2 (amide carbonyl). Elemental analysis of PQNNDAP: Calculated 48.67%C, 9.08% N, 2.30% Cl; Found 49.61% C, 8.40% N, 2.36% Cl.

CMCNNDAP (0.1840 g) was dissolved in 10 ml of dimethylamine (DMA) in a3-neck, round bottom flask, equipped with a magnetic stir bar,water-cooled condenser, and thermometer. After dissolution, EPC (1 ml)was added, and the temperature rose to 75° C. After a few minutes thetemperature dropped and the reaction mixture became very viscous. Then 2ml each of DMA and EPC were added daily for 3 days, and reactioncontinued at a temperature maintained between 40-50° C. The very viscousreaction mixture was dialyzed for 3 days against distilled water, andwas then freeze-dried; 1.5747 g of product, PQNNDAP, was obtained. ¹ HNMR (D₂ O), δ (ppm): 3.25-4.5 (broad overlapping peaks of anhydroglucosering); 4.9 (s, broad); 3.6-3.4 (d,s,s overlapping); 3.3 (s), 3.2 (s).

Standardization of Potassium Polyvinylsulfate (PVSK) and Sodium DodecylSulfate (SDS). Stock solutions of cetylpyridinium chloride monohydrate(CPM), 0.8010 g; potassium polyvinylsulfate (PVSK), 0.0405 g; and sodiumdodecyl sulfate (SDS), 0.6837 g; respectively were prepared bydissolving in 1000 ml of distilled water. PVSK (2.50×10⁴ M), and SDS(2.37×10⁻³ M) solutions were used as the anionic titrants. SDS and PVSK,25 ml aliquots, were standardized by 2.24×10⁻³ M CPM using two drops of1% toluidine blue indicator. The transmittance at 420 nm was measuredwith a spectrometer. During the titration, the solutions became cloudyand coagulated. The color changed from blue to purple, and at theendpoint to red-wine.

Differential Scanning Calorimetry ("DSC"). A Seiko DSC220C was used forthermal analysis of the aminoamide cellulosics. The glass transitiontemperature was observed after the aminoamide cellulosics were subjectedto a cooling/heating cycle (25° C. to 125° C.) at 10° C./min. Theaminoamides were also subjected to a cooling/heating cycle (125° C. to500° C.) at a heating rate of 5° C./min to observe any othertransitions. Both cooling/heating cycles were carried out in a nitrogenatmosphere.

Thermogravimetric Analysis ("TGA."). A Seiko TG/DTA 220 was used toobserve the thermal stability of the aminoamide cellulosics. Thederivatives were subjected to a two step analysis. The first heatingcycle (25° C. to 130° C.) dried the cellulosics, and the second step(25° C. to 500° C.) was used to observe the thermal decomposition. Theheating cycles were performed at 5° C./min in nitrogen.

Miscellaneous. The cellulosic derivatives of the present invention maybe incorporated into hair care products of otherwise conventionalformulation, but with lower levels of VOC's. For example a hairspray, inaddition to the novel polymer, will typically contain plasticizers togive film flexibility and to modify adhesion, about 5% weight/volume,for example silicones, esters (e.g., isopropyl myristate), polyols(e.g., glycerol); softening agents, for example lanoline or lanolinederivatives; glossing agents to add shine, for example silicones;perfumes to cover the odor of the other components; solvents to spreadthe film and control drying rate, for example ethanol, isopropanol, orwater; and propellants (about 40-70% of the total weight), for examplebutane, isobutane, or propane.

One example of a hairspray formulation follows: (1) polymer inaccordance with the present invention, 1-4%; (2) lanolin, 0.05-0.25%;(3) silicone, 0.10-0.25.%; (4) isopropyl myristate, 0.05-0.50%; (5)perfume, 0.05-0.25%; (6) isopropanol, 10-50%; (7) isobutane, 40-70%.

When used as a thickener in gels, polymers in accordance with thepresent invention may be present between about 1% and about 20% byweight, preferably about 5%. The other components of a typical gel mayfor example be the following: polyethylene glycol, about 30%;isopropanol, about 25%; water, about 40%.

These formulations work well with VOC levels below about 30%, comparedto current formulations that typically use up to 50% VOC's. As the novelpolymers are water soluble, it would also be possible to use water asthe sole solvent, without any VOC's, if desired. However, drying timesfor the formulations would be adversely affected. Even if VOC's areused, the levels are substantially lower than is required for currentlyused compounds. Even 10% ethanol greatly reduces the drying time of aformulation.

Typical components of shampoos include surfactants, foam boosters,conditioning agents, preservatives, sequestering agents, polymericviscosity modifiers, opacifying or clarifying agents, water, fragrance,coloring agents, stabilizers (e.g., antioxidants, ultravioletabsorbers), and optional specialty additives. One example of a shampooformulation using the compounds of the present invention follows: sodiumlauryl sulfate, about 10%; lauric diethanolamide, about 5%; hexyleneglycol, about 3%; methyl p-hydroxy benzoate, about 0.1%; sodiumchloride; stearic acid or boric acid, about 1%; cationic cellulosicderivative, about 0.5%; ethanol, about 15%; water to 100%.

Another example of a shampoo formulation in accordance with the presentinvention, a 2-in-1 conditioning shampoo, is the following: coconutamidopropyl-3-dimethylamino betaine, about 5.5%; sodium laurel sulfate,about 5%; ethanol, about 15%; cationic cellulose polymer, about 1%;perfume, about 0.5%; methyl-p-hydroxybenzoate (preservative), about0.25%; antioxidant, about 0.25%; EDTA (sequestering agent), about 0.05%;water, to 100%.

Other uses for the novel polymers include conditioners, mousses,spritzes, hot oil treatments, detanglers, conditioning hair masks, haircolors, permanent wave products, and leave-in conditioners. The polymersmay be used in formulations that are otherwise in accordance withformulations known in the art, preferably with lower levels of VOC's.See, e.g., J. B. Wilkinson et al. (eds.), Harry's Cosmeticology, Chem.Publishing, New York (1982).

The complete disclosures of all references cited in this specificationare hereby incorporated by reference. In the event of an otherwiseirreconcilable conflict, however, the present specification shallcontrol.

We claim:
 1. A method for killing bacteria or inhibiting the growth ofbacteria, comprising applying to the bacteria a carboxymethyl cellulosederivative, wherein some or all of the sites normally occupied bycarboxymethyl groups are occupied by diquaternary ammonium groups of theformula ##STR12## wherein there are at least about 0.2 said diquaternaryammonium groups present for each anhydroglucose unit of said cellulosederivative; and wherein:R¹ is hydrogen or methyl; R² is a divalentaliphatic hydrocarbon group with 2 to 20 carbon atoms; R³, R⁴, R⁶, R⁷,and R⁸ are alkyl groups with 1 to 4 carbon atoms that may be the same asone another or different from one another; R⁵ is a substituted orunsubstituted divalent aliphatic group with 2 to 5 carbon atoms; and X¹and X² are anions that may be the same as one another or different fromone another.
 2. A method as recited in claim 1, wherein there arebetween about 0.3 and about 0.7 said diquaternary ammonium groupspresent for each anhydroglucose unit of said cellulose derivative; andwherein:R¹ is hydrogen; R² is --CH₂ --CH₂ -- or --CH₂ --CH₂ --CH₂ --;R³, R⁴, R⁶, R⁷, and R⁸ are each methyl groups; R⁵ is --CH₂ --CH(OH)--CH₂--; and X¹ and X² are may be the same as one another or different fromone another, and are each a halide, a sulfate ester group, or a sulfonicacid group.
 3. A method as recited in claim 2, wherein there are about0.5 said diquaternary ammonium groups present for each anhydroglucoseunit of said cellulose derivative; wherein R² is --CH₂ --CH₂ --; andwherein X¹ and X² are each chloride.
 4. A method for killing bacteria orinhibiting the growth of bacteria, comprising applying to the bacteria acarboxymethyl cellulose derivative, wherein some or all of the sitesnormally occupied by carboxymethyl groups are occupied by polyquaternaryammonium groups of the formula ##STR13## wherein there are at leastabout 0.2 said diquaternary ammonium groups present for eachanhydroglucose unit of said cellulose derivative; wherein b is between 2and 8; and wherein:R¹ is hydrogen or methyl; R² is a divalent aliphatichydrocarbon group with 2 to 20 carbon atoms; R³, R⁴, R⁶, R⁷, and R⁸ arealkyl groups with 1 to 4 carbon atoms that may be the same as oneanother or different from one another; R⁵ is a substituted orunsubstituted divalent aliphatic group with 2 to 5 carbon atoms; and X¹and X² are anions that may be the same as one another or different fromone another.
 5. A method as recited in claim 4, wherein there arebetween about 0.3 and about 0.7 said diquaternary ammonium groupspresent for each anhydroglucose unit of said cellulose derivative;wherein b is 4 or 5; and wherein:R¹ is hydrogen; R² is --CH₂ --CH₂ -- or--CH₂ --CH₂ --CH₂ --; R³, R⁴, R⁶, R⁷, and R⁸ are each methyl groups; R⁵is --CH₂ --CH(OH)--CH₂ --; and X¹ and X² are may be the same as oneanother or different from one another, and are each a halide, a sulfateester group, or a sulfonic acid group.
 6. A method as recited in claim5, wherein there are about 0.5 said diquaternary ammonium groups presentfor each anhydroglucose unit of said cellulose derivative; wherein b is4; wherein R² is --CH₂ --CH₂ --; and wherein X¹ and X² are eachchloride.